US9938374B2 - Zinc catalyst/additive system for the polymerization of epoxide monomers - Google Patents

Zinc catalyst/additive system for the polymerization of epoxide monomers Download PDF

Info

Publication number
US9938374B2
US9938374B2 US15/035,411 US201415035411A US9938374B2 US 9938374 B2 US9938374 B2 US 9938374B2 US 201415035411 A US201415035411 A US 201415035411A US 9938374 B2 US9938374 B2 US 9938374B2
Authority
US
United States
Prior art keywords
catalyst
alcoholate
alcohol
polymerization
metal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
US15/035,411
Other languages
English (en)
Other versions
US20160280853A1 (en
Inventor
Anna V. Davis
Peter N. Nickias
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Chemical Co
Nutrition and Biosciences USA 1 LLC
Original Assignee
Dow Global Technologies LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dow Global Technologies LLC filed Critical Dow Global Technologies LLC
Priority to US15/035,411 priority Critical patent/US9938374B2/en
Publication of US20160280853A1 publication Critical patent/US20160280853A1/en
Assigned to DOW GLOBAL TECHNOLOGIES LLC reassignment DOW GLOBAL TECHNOLOGIES LLC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: DAVIS, Anna V., NICKIAS, PETER N.
Application granted granted Critical
Publication of US9938374B2 publication Critical patent/US9938374B2/en
Assigned to DDP SPECIALTY ELECTRONIC MATERIALS US, LLC. reassignment DDP SPECIALTY ELECTRONIC MATERIALS US, LLC. CHANGE OF LEGAL ENTITY Assignors: DDP Specialty Electronic Materials US, Inc.
Assigned to THE DOW CHEMICAL COMPANY reassignment THE DOW CHEMICAL COMPANY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: DOW GLOBAL TECHNOLOGIES LLC
Assigned to DDP Specialty Electronic Materials US, Inc. reassignment DDP Specialty Electronic Materials US, Inc. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: THE DOW CHEMICAL COMPANY
Assigned to NUTRITION & BIOSCIENCES USA 1, LLC reassignment NUTRITION & BIOSCIENCES USA 1, LLC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: DDP SPECIALTY ELECTRONIC MATERIALS US, LLC.
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
    • C08G65/269—Mixed catalyst systems, i.e. containing more than one reactive component or catalysts formed in-situ
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0201—Oxygen-containing compounds
    • B01J31/0211—Oxygen-containing compounds with a metal-oxygen link
    • B01J31/0212—Alkoxylates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • B01J31/146—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of boron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C08G59/681—Metal alcoholates, phenolates or carboxylates
    • C08G59/682—Alcoholates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
    • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
    • C08G65/08—Saturated oxiranes
    • C08G65/10—Saturated oxiranes characterised by the catalysts used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
    • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
    • C08G65/08—Saturated oxiranes
    • C08G65/10—Saturated oxiranes characterised by the catalysts used
    • C08G65/12—Saturated oxiranes characterised by the catalysts used containing organo-metallic compounds or metal hydrides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
    • C08G65/2645—Metals or compounds thereof, e.g. salts
    • C08G65/2654—Aluminium or boron; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
    • C08G65/2645—Metals or compounds thereof, e.g. salts
    • C08G65/266—Metallic elements not covered by group C08G65/2648 - C08G65/2645, or compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/10—Polymerisation reactions involving at least dual use catalysts, e.g. for both oligomerisation and polymerisation
    • B01J2231/14—Other (co) polymerisation, e.g. of lactides or epoxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
    • B01J2531/26—Zinc

Definitions

  • the present invention relates to a new catalyst formulation comprising a zinc alcoholate catalyst in combination with a metal alcoholate additive.
  • the catalyst formulation can be used to polymerize an epoxide monomer, for example ethylene oxide.
  • catalysts are known for the ring opening polymerization of epoxide monomers such as ethylene oxide.
  • Examples of catalysts systems that are used for the industrial-scale production of poly(ethylene oxide) include calcium-based and zinc-based types of catalysts.
  • EP 0 239 973 A2 relates to zinc alkoxide and zinc aryloxide catalysts prepared from the reaction of a hydrocarbyl compound of zinc with a dispersion of a polyol in an inert medium. It is taught that the use of a dispersion aid such as fumed silica, magnesia or alumina and a nonionic solvent are critical to achieving good dispersion of the polyol in the inert medium. In this way fine catalyst particles are created.
  • Preferred are linear polyols having from 2 to 6 carbon atoms in the alkane chain (most preferred having 4 carbon atoms) or a cycloalkane diol having 5 or 6 ring carbon atoms.
  • Dispersion prepared catalysts are useful in the polymerization of cyclic alkylene oxides, e.g. ethylene oxide and propylene oxide, to produce high molecular weight polymers and copolymers.
  • U.S. Pat. No. 4,667,013 A describes as process for polymerizing alkylene oxides in the presence of a catalyst dispersion similar to that in EP 0 239 973 A2 above wherein a hydrogen-containing chain transfer agent having a pk a value of from 9 to 22 is added to the polymerizing mixture to control the molecular weight of the resulting polymer.
  • the chain transfer agent is preferably an alkanol (aliphatic alcohol) having from 1 to 16 carbon atoms.
  • U.S. Pat. No. 6,084,059 A details the preparation of metal alcoholate catalysts (including zinc alcoholates) wherein an organometallic compound is reacted with water or a active-hydrogen-containing compound such as an aliphatic polyol using a micelle or reversed-micelle technique facilitated by an ionic surfactant.
  • anionic surfactants is said to be most effective at promoting formation of micelles or reversed micelles which are subsequently reacted with the organometallic reagent such as diethylzinc to form an especially active catalyst. It is taught that the use of dispersion promoters such as fumed silica is not essential.
  • U.S. Pat. No. 5,326,852 A concerns the production of alkylene oxide polymers in the presence of a catalyst which is obtained by first reacting a hydrocarbyl compound of zinc with an aliphatic polyhydric alcohol, then reacting the product with a monohydric alcohol having 1 to 6 carbon atoms and finally applying a heat treatment at 80 to 200° C.
  • U.S. Pat. No. 6,979,722 B2 teaches the polymerization of an alkylene oxide in the presence of a catalyst in a branched aliphatic hydrocarbon solvent having 5 to 7 carbon atoms wherein the catalyst is a zinc compound obtained by the reaction of an organic zinc compound and an alcohol.
  • the catalyst is prepared by first reacting diethyl zinc with 1,4-butanediol and then with ethanol.
  • U.S. Pat. No. 3,607,785 A and DE 1 808 987 A describe the preparation of a catalyst by first reacting an Al alkoxide with Zn acetate and then contacting the resulting catalyst with a primary alcohol RCH 2 OH. There is no mention of zinc alcoholates derived from polyols. In the examples, the catalyst is used to polymerize propylene oxide.
  • U.S. Pat. No. 3,459,685 A teaches the polymerization of alkylene oxides with a catalyst system of a polymeric Al alcoholate and an organometallic compound, for example methyl zinc phenoxide is mentioned. There is no mention of zinc alcoholates derived from polyols.
  • U.S. Pat. No. 3,542,750 A is directed to the polymerization of alkylene oxides with a catalyst system of (a) the condensation product of Al hydroxide with an Al alcoholate and (b) an organometallic compound, for example methyl zinc phenoxide.
  • a catalyst system of (a) the condensation product of Al hydroxide with an Al alcoholate and (b) an organometallic compound, for example methyl zinc phenoxide.
  • an organometallic compound for example methyl zinc phenoxide.
  • DE 1 667 275 A and GB 1,197,986 A disclose a catalyst composition for the polymerization of alkylene oxide which composition comprises the reaction product of a partially hydrolyzed Al alkoxide and a group II or III organometallic compound.
  • the organometallic compound is preferably diethyl zinc. There is no mention of zinc alcoholates derived from polyols.
  • DE 1 937 728 A relates to a process for polymerizing alkylene oxide by contacting it with a catalyst prepared by reacting (1) an Al alkoxide with (2) phosphoric acid or an phosphoric acid monoester or diester, (3) an aliphatic alcohol and/or (4) a group II or III organometallic compound such as for example diethyl zinc.
  • a catalyst prepared by reacting (1) an Al alkoxide with (2) phosphoric acid or an phosphoric acid monoester or diester, (3) an aliphatic alcohol and/or (4) a group II or III organometallic compound such as for example diethyl zinc.
  • zinc alcoholates derived from polyols There is no mention of zinc alcoholates derived from polyols.
  • Zinc-based systems are also described as catalysts for the addition reaction of alkylene oxides with alkanols.
  • U.S. Pat. No. 4,375,564 A is directed to the preparation of low molecular weight alkanol alkoxylates having 1 to 30 alkylene oxide units.
  • the catalyst system employed is a combination of a first component of a soluble basic compound of Mg and a second component of a soluble basic compound of an element selected from various metals including Zn.
  • the preferred Mg compounds are Mg alkoxides, preferably having 1 to 30 carbon atoms.
  • the preferred second component is a metal alkoxide, preferably having 1 to 30 carbon atoms, more preferably 1 to 6 carbon atoms, most preferred 2 or 3 carbon atoms. Alcoholates derived from polyols are not mentioned.
  • the problem addressed by the present invention is to provide a new catalyst formulation that allows for the polymerization of epoxide monomers such as ethylene oxide to access a greater range of product polymer molecular weights including lower molecular weights than would be achievable with a zinc alkoxide catalyst alone.
  • a Zn catalyst comprising a Zn compound having alcoholate ligand(s) derived from one or more polyols
  • a catalyst additive comprising a metal compound (i) having alcoholate ligand(s) derived from one or monohydric alcohol wherein the metal is selected from:
  • the present invention also relates to the use of the above defined Zn catalyst in combination with the above defined catalyst additive in the polymerization of an epoxide monomer, preferably ethylene oxide.
  • the present invention is directed to a process for polymerizing an epoxide monomer, preferably ethylene oxide, comprising carrying out the process in the presence of the above defined Zn catalyst and the above defined catalyst additive.
  • FIG. 1 illustrates the EO polymerizations described in Examples 3 and 8.
  • the inventive catalyst formulation comprises (a) a Zn catalyst component and (b) a catalyst additive component which comprises a metal compound (i) as defined above and optionally (ii) an alcohol and/or water.
  • Zn compound and metal compound as used herein are not restricted to a certain type of bonding between the metal and the “ligand(s)” and include coordination compounds, ionic compounds and covalent compounds with no definitive distinction between each type of bonding.
  • Zn alcoholate”, “Zn complex”, “metal alcoholate”, and “metal complex” are not restricted to compounds having a certain type of bonding between the metal and the “ligand(s)” and the bonds may have coordinative, ionic and/or covalent character.
  • ligand is not restricted to true ligands in the narrower sense that are bonded to a central metal atom or ion by coordinative bonding to form a true complex compound, but the term “ligand” is herein used to describe the moiety that is bound to the metal by bonds that may have coordinative, ionic and/or covalent character.
  • the Zn catalyst (a) comprises a Zn compound having alcoholate ligand(s) derived from one or more polyols (polyhydric alcohols).
  • the Zn compound is typically selected from:
  • the polyol from which the alcoholate ligand(s) is/are derived is typically a diol although higher polyols such as triols, e.g. glycerine, may also be suitable.
  • the polyol, preferably diol is preferably aliphatic or cycloaliphatic (preferably having 5 or 6 ring carbon atoms) or mixed aliphatic/cycloaliphatic comprising both aliphatic and cycloaliphatic moieties (preferably having 5 or 6 ring carbon atoms).
  • the polyol, preferably diol is an aromatic polyol including mixed aliphatic/aromatic polyols comprising both aliphatic and aromatic moieties.
  • the polyol preferably diol, may comprise a hydrocarbon backbone with heteroatoms such as O and/or Si (e.g. polyether polyols such as polyalkylene polyols) in its backbone or heteroatoms such as O, Si and/or halogen, e.g. F, as part of functional groups (e.g. methoxy or trifluoromethyl groups) pendant from the backbone.
  • the Zn compound has alcoholate ligand(s) derived from one or more alkanediols (which can be straight-chain or branched).
  • the diol preferably the alkanediol, has 2 to 8 carbon atoms directly linking the oxygen atoms of the hydroxyl groups, more preferably 2 to 6 carbon atoms directly linking the oxygen atoms and most preferably 4 carbon atoms directly linking the oxygen atoms.
  • suitable diols include ethylene glycol; diethylene glycol; triethyleneglycol; 1,2-propanediol; 1,3-propanediol; 1,4-butanediol; 1,3-butanediol; 1,5-pentanediol; 1,6-hexanediol; 1,2-cyclopentanediol (cis- and trans-); 1,2-cyclohexanediol (cis- and trans-); 1,2-cyclohexanedimethanol (cis- and trans-); 1,2-benzenedimethanol; (2,5-hexanediol (RR-, RS-, and SS-); 2,5-dimethyl-2,5-hexanediol (RR-, RS-, and SS-); with 1,4-butanediol being especially preferred.
  • the polyol-derived alcoholate ligand(s) of the Zn compound constituting the Zn catalyst (a) can be derived from a single polyol or a mixture of at least two different polyols.
  • the Zn alcoholate (a1) can either be a homoleptic Zn alcoholate only comprising one type of alcoholate ligand(s) or a heteroleptic Zn alcoholate comprising at least two types of alcoholate ligands derived from at least two different polyols, typically two different diols.
  • the Zn compound (including the Zn alcoholate (a1) and the heteroleptic Zn alcoholate (a2)) has alcoholate ligand(s) that are derived from a single polyol, typically a single diol.
  • the Zn alcoholate (a1) is a homoleptic or heteroleptic Zn alcoholate of any of the polyols as defined above including the preferred embodiments.
  • the Zn alcoholate (a1) is homoleptic.
  • the heteroleptic Zn alcoholate comprises alcoholate ligand(s) derived from one or more monohydric alcohols and/or water in addition to alcoholate ligand(s) derived from polyol(s) as defined above including the preferred embodiments.
  • (a2) is heteroleptic Zn alcoholate of one ore more polyols and one or more monohydric alcohols, i.e. the heteroleptic Zn alcoholate (a2) comprises alcoholate ligand(s) derived from one or more polyols and alcoholate ligand(s) derived from one or more monohydric alcohols.
  • the monohydric alcohol is a monohydric aliphatic alcohol including monohydric halosubstituted aliphatic alcohols.
  • the monohydric alcohol is an alkanol (which can be straight-chain or branched), more preferably a C 1 to C 10 alkanol, and most preferably a C 1 to C 4 alkanol.
  • Lower alkanols such as C 1 to C 4 alkanols are advantageous because they are volatile and can be easily removed from the Zn catalyst during preparation.
  • suitable monohydric alcohol from which the alcoholate ligand(s) in the heteroleptic Zn alcoholate (a2) is/are derived include methanol; ethanol; 1-propanol; 2-propanol; 1-butanol; 2-butanol; tert-butyl alcohol; iso-butyl alcohol; 1-pentanol; 2-pentanol; 3-pentanol; 1-hexanol; 2-hexanol; 3-hexanol; 2-ethyl hexanol; 1-heptanol; 2-heptanol; 3-heptanol; 4-heptanol; 4-methyl-3-heptanol; 2,6-dimethyl-4-heptanol; 1-octanol; 2-octanol; 3-octanol; 4-octanol; 1-methoxy-2-propanol; cyclohexanol; 4-tert-butyl-cycl
  • the monohydric alcoholate ligand(s) of the heteroleptic Zn alcoholate (a2) can be derived from a single monohydric alcohol or a mixture of at least two different monohydric alcohols. If water is contained in the heteroleptic Zn alcoholate (a2) it is believed that it is incorporated as a hydroxide, such as a terminal hydroxide or as an oxide which may bridge two zinc centers.
  • the monohydric alcoholate ligand(s) of the heteroleptic Zn alcoholate (a2) are derived from a single monohydric alcohol, more preferably from ethanol.
  • the Zn catalyst (a) is a heteroleptic Zn alcoholate (a2) of 1,4-butanediol and a C 1 to C 4 alkanol such as ethanol.
  • Zn compounds (a1), (a2), and (a3) including those preferred Zn compounds mentioned above are often complex and difficult to resolve. This especially applies to the heteroleptic Zn complexes. Zn complexes having alcoholate ligands are frequently dimeric, oligomeric or even polymeric in structure with sometimes poorly defined structures and may experience transformations between different structures. Bridging of two Zn atoms by one oxygen is known to occur. Thus, the Zn compounds (a1), (a2), and (a3) described herein explicitly include monomeric, dimeric, oligomeric and polymeric species.
  • heteroleptic Zn alcoholate (a2) e.g. derived from one diol and one monohydric alcohol or two different diols and one monol, or one diol and two different monohydric alcohols
  • the product may contain a combination of heteroleptic and homoleptic Zn alcoholates.
  • the Zn catalyst (a) of the present invention may comprise one single Zn compound having alcoholate ligand(s) derived from one or more polyols, preferably selected from those Zn compounds (a1) and (a2) as described above, or a mixture of at least two different Zn compounds, preferably selected from those Zn compounds (a1) and (a2) as described above.
  • the Zn catalyst (a) comprises a Zn alcoholate (a1) of one or more polyols as described above and a Zn alcoholate (a3) of one or more monohydric alcohols wherein the monohydric alcohols are as defined above for the heteroleptic Zn alcoholate (a2).
  • the Zn alcoholate (a1) of one or more polyols and the Zn alcoholate (a3) of one or more monohydric alcohols are often combined with a heteroleptic Zn alcoholate (a2) of one or more polyols and one or more monohydric alcohols wherein the alcoholate ligand(s) are derived from the same polyol(s) and monohydric alcohol(s) as in the Zn alcoholate (a1) of one or more polyols and the Zn alcoholate (a3) of one or more monohydric alcohols.
  • the Zn alcoholates (a1) of the present invention are typically produced by reacting a dihydrocarbyl Zn compound with one or more polyols as specified above.
  • the dihydrocarbyl zinc compounds are preferably the alkyls and aryls of the general formula R 2 Zn in which R is (1) an alkyl group containing from 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms, and most preferably 2 or 3 carbon atoms, or (1) phenyl or naphthyl or alkyl-substituted phenyl or naphthyl groups in which the alkyl groups contain from 1 to 4 carbon atoms, preferably 1 to 3 carbon atoms, or (3) cycloalkyl groups containing from 4 to 6 ring carbon atoms; or (iv) the dicyclopentadienyl group.
  • Illustrative thereof are dimethylzinc, diethylzinc, di-n-propylzinc, di-isopropylzinc, dibutylzinc (di-n-butylzinc, di-isobutylzinc, di-t-butylzinc), dipentlyzinc, dihexyl- and diheptyl- and dioctylzinc, di-2-ethylhexylzinc, diphenylzinc, ditolylzinc, dicyclobutylzinc, dicyclopentylzinc, di-methylcyclopentylzinc, dicyclohexylzinc, methyl phenylzinc, methyl tolylzinc, methyl naphthylzinc, and ethyl phenylzinc.
  • the nature of the zinc compounds is not critical but those possessing some solubility in the reaction medium employed is advantageous.
  • the use of a linear dialkylzinc as the starting material for the Zn alkoxide preparation is preferred, diethyl zinc being most preferred.
  • Exemplary preparation routes to Zn alcoholates (a1) are taught in EP 0 239 973 A2, U.S. Pat. No. 5,326,852 A and U.S. Pat. No. 6,084,059 A.
  • the heteroleptic Zn alcoholates (a2) of the present invention are typically prepared by reacting a dihydrocarbyl Zn compound as described above with one or more polyols as specified above and one or more monohydric alcohols as specified above. Although it is preferred to react first the dihydrocarbyl Zn compound with the polyol(s), followed by a reaction with the monohydric alcohol(s), the order of reaction may be inverted or a mixture of all three components may be reacted simultaneously. Regardless of how the components are reacted the reaction can be completed by a heat treatment step such as at 80 to 200° C. for 5 to 180 min which is typically carried out while distilling off the unreacted alcohols.
  • a heat treatment step such as at 80 to 200° C. for 5 to 180 min which is typically carried out while distilling off the unreacted alcohols.
  • the equivalent ratio of polyol to dihydrocarbyl Zn compound is typically 0.2:1 to 1.1:1 and preferably 0.5:1 to 0.95:1.
  • the equivalent ratio of monohydric alcohol to dihydrocarbyl Zn compound is typically at least 0.1:1 and preferably 0.1:1 to 1.5:1.
  • stoichiometry should be carefully controlled to limit excess alcohol relative to zinc-C bonds.
  • a corresponding preparation method of heteroleptic Zn alcoholates (a2) is taught in more detail in U.S. Pat. No. 5,326,852 A.
  • 6,979,722 B2 describes in Example 1 the preparation of a heteroleptic Zn alcoholate (a2) from diethylzinc (1.0 molar equivalents), 1,4-butanediol (0.8 molar equivalents), and ethanol (1.3 molar equivalents) in hydrocarbon solvent.
  • the final catalyst is a white slurry.
  • the Zn alcoholates (a3) of one or more monohydric alcohols are typically produced in a manner similar to that described for compounds (a2) with a stoichiometry of 2.0 equivalents of monohydric alcohol to dialkylzinc reagent. In the case that excess monohydric alcohol is used, volatile alcohols are preferred to facilitate removal of unreacted material.
  • the Zn compounds (a1), (a2) and (a3) may be obtained as an isolated solid powder (as for example described in EP 0 239 973 A2 and U.S. Pat. No. 5,326,852 A) or in the form of a slurry (as for example described in U.S. Pat. No. 6,979,722 B2) in solvent which slurry may be employed directly in the polymerization reaction.
  • the catalyst additive component (b) comprises a metal compound (i) having alcoholate ligand(s) derived from one or monohydric alcohol and wherein the metal is selected from:
  • (I) group 13 metals such as B, Al, Ga, and In, preferably Al,
  • the monohydric alcohol from which the alcoholate ligand(s) of the metal compound (i) is/are derived is typically aliphatic or cycloaliphatic (preferably having 5 or 6 ring carbon atoms) or mixed aliphatic/cycloaliphatic comprising both an aliphatic and cycloaliphatic moieties (preferably having 5 or 6 ring carbon atoms).
  • the monohydric alcohol is an aromatic alcohol including mixed aliphatic/aromatic alcohols comprising both aliphatic and aromatic moieties.
  • alcohol explicitly includes phenols.
  • the monohydric alcohol may comprise a hydrocarbon backbone with heteroatoms such as O and/or Si in its backbone or heteroatoms such as O, Si and/or halogen, e.g. F, as part of functional groups (e.g. methoxy or trifluoromethyl groups) pendant from the backbone.
  • the monohydric alcohol is an aliphatic alcohol, more preferably an alkanol (which can be straight-chain or branched), and even more preferably an alkanol comprising 1 to 20 carbon atoms, most preferably 3 to 12 carbons atoms.
  • monohydric alcohols include ethanol, 1-propanol (n-propyl alcohol), 2-propanol (iso-propyl alcohol), 1-butanol (n-butyl alcohol), 2-methyl-1-propanol (iso-butyl alcohol), 2-butanol (sec-butyl alcohol), 2-methyl-2-propanol (t-butyl alcohol), 2-ethylhexanol, octanol, nonanol, methoxypropanol, phenol, and methylphenols.
  • the monohydric alcoholate ligand(s) of the metal compound (i) can be derived from a single monohydric alcohol or a mixture of at least two different monohydric alcohols.
  • the monohydric alcoholate ligand(s) of the metal compound (i) are derived from a single monohydric alcohol.
  • the metal compound (i) comprises only alcoholate ligand(s), i.e. the metal compound (i) is a metal alcoholate (b1) of one or more monohydric alcohols.
  • the metal compound (i) comprises non-alcoholate ligand(s) in addition to the alcoholate ligand(s), i.e. the metal compound (i) is a heteroleptic metal complex (b2) having alcoholate ligand(s) derived from one or more monohydric alcohols and non-alcoholate ligand(s).
  • suitable non-alcoholate ligands include ethylacetoacetate ligand(s) and 2,4-pentanedionate ligand(s).
  • the heteroleptic metal complex (b2) can comprises one single type of non-alcoholate ligand or mixtures of at least two different non-alcoholate ligands.
  • the heteroleptic metal complex (b2) comprises only one type of non-alcoholate ligand.
  • Preferred embodiments of the metal compound (i) comprise the preferred alcoholate and/or non-alcoholate ligand(s) in combination with the preferred metals as described above.
  • metal compounds (b1) and (b2) which may be used in the catalyst additive (b) of the present catalyst formulation are aluminum tri-sec-butoxide, aluminum tri-n-butoxide, aluminum (di-s-butoxide) ethylacetoacetate, and di-s-butoxyaluminoxy-triethoxysilane ((s-BuO) 2 —Al—O—Si(OEt) 3 ).
  • the structures of the metal compounds (b1) and (b2) including those preferred metal compounds (b1) and (b2) mentioned above are often complex and difficult to resolve. This especially applies to the heteroleptic metal complexes.
  • Metal complexes having alcoholate ligands are frequently dimeric, oligomeric or even polymeric in structure with sometimes poorly defined structures and may experience transformations between different structures. Bridging of two metal atoms by one oxygen is known to occur (e.g. in di-s-butoxyaluminoxy-triethoxysilane).
  • the metal compounds (b1) and (b2) described herein explicitly includes monomeric, dimeric, oligomeric and polymeric species.
  • the catalyst additive (b) of the present invention may comprise a single metal compound (i) or a mixture of different metal compounds (i).
  • metal compounds (b1) and (b2) are commercially available. Others can be prepared by routes such as reaction of hydrocarbyl metal precursors (such as triethylaluminum) with the appropriate stoichiometries of monohydric alcohol, or salt metathesis of the alkali salt (e.g. Li) of the deprotonated monohydric alcohol with the precursor metal chloride of interest.
  • hydrocarbyl metal precursors such as triethylaluminum
  • salt metathesis of the alkali salt (e.g. Li) of the deprotonated monohydric alcohol with the precursor metal chloride of interest e.g. Li
  • the metal compounds (i), including metal compounds (b1) and (b2) are soluble in a hydrocarbon solvent. Their preparation may result in a solution of the metal compound (i) in a hydrocarbon solvent which solution may be employed directly in the polymerization reaction.
  • the catalyst additive (b) may further contain an alcohol (ii) as an optional component.
  • an alcohol ii
  • the term “alcohol” is used herein in contrast to the term “alcoholate” and designates an alcohol which is not deprotonated.
  • the alcohol (ii) is an aliphatic, cycloaliphatic or aromatic alcohol. It is preferred that the alcohol is monohydric.
  • the alcohol is preferably an aliphatic, cycloaliphatic (preferably having 5 or 6 ring carbon atoms) or mixed aliphatic/cycloaliphatic alcohol comprising both an aliphatic and cycloaliphatic moiety (preferably having 5 or 6 ring carbon atoms); an aromatic alcohol or a mixed aliphatic/aromatic alcohol comprising both aliphatic and aromatic moieties.
  • the alcohol typically the monohydric alcohol, is an alkanol (which can be straight-chain or branched) and even more preferably, an alkanol comprising 1 to 20 carbon atoms, and most preferably 4 to 12 carbons atoms.
  • alkanols include methanol, ethanol, 1-propanol (n-propyl alcohol, 2-propanol (iso-propyl alcohol), 1-butanol (n-butyl alcohol), 2-butanol (sec-butyl alcohol), 2-methyl-1-propanol (iso-butyl alcohol), 2-methyl-2-propanol (tert-butyl alcohol, 2-ethylhexanol, and octanol.
  • the catalyst additive (b) may comprise a single alcohol (ii) or a mixture of different alcohols (ii).
  • the alcohol (ii) that is used in the catalyst composition (b) in addition to the metal compound (i) may be the same as the alcohol from which the alcoholate ligand(s) in metal compound (i) is/are derived. However, it is not mandatory that the alcohol (ii) corresponds to the alcoholate ligand(s) of metal compound (i).
  • the alcohol (ii) is bound to the metal compound (i)/the metal of the metal compound (i).
  • the alcohol (ii) forms an adduct with the metal compound (i).
  • a variety of alcohol adducts of metal alcoholates (b1) is commercially available.
  • the alcohol (ii) is added to the metal compound (i) to become a component of the catalyst additive (b).
  • the alcohol (ii) may also be formed in situ by adding water to the metal compound (i) to react with part of the alcoholate ligand(s) of the metal compound (i), typically metal alcoholate (b1).
  • the Zn alkoxide catalyst (a) can be used together with the catalyst additive (b) in a conventional process for polymerizing an epoxide, typically in a suspension polymerization process.
  • the novel catalyst formulation of this invention is useful in effecting the polymerization of epoxide monomers which contain a cyclic group composed of two carbon atoms and one oxygen atom.
  • these epoxide monomers can be characterized by the following formula:
  • each R 1 individually, can be hydrogen, haloaryl, or a hydrocarbon radical free from ethylenic and acetylenic unsaturation such as, for example, alkyl, aryl, cycloalkyl, aralkyl, or alkaryl radicals.
  • both R 1 variables together with the epoxy carbon atoms, i.e.
  • the carbon atoms of the epoxy group can represent a saturated cycloaliphatic hydrocarbon nucleus which contains from 4 to 10 carbon atoms, preferably from 4 to 8 carbon atoms, for example, a saturated cycloaliphatic hydrocarbon nucleus derived from cycloalkane, alkyl substituted cycloalkane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, methylcyclopentane, or amylcyclohexane.
  • R 1 radicals include, among others, methyl, ethyl, propyl, butyl, isobutyl, hexyl, isohexyl, 3-propylheptyl, dodecyl, octadecyl, phenyl, halophenyl, chlorophenyl, bromophenyl, benzyl, tolyl, ethylphenyl, butylphenyl, phenethyl, phenylpropyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, and cycloheptyl.
  • a single epoxide monomer or an admixture of at least two different epoxide monomers can be employed as the monomeric feed.
  • a broad range of epoxide monomers can be used in the polymerization process and representative expoxide monomers include, for example, ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, the epoxypentanes, the epoxyhexanes, 2,3-epoxyheptane, nonene oxide, 5-butyl-3,4-epoxyoctane, 1,2-epoxydodecane, 1,2-epoxyhexadecane, 1,2-epoxyoctadecane, 5-benzyl-2,3-epoxyheptane, 4-cyclo-hexyl-2,3-epoxypentane, chlorostyrene oxide, styrene oxide, ortho-, meta-, and para-ethylstyrene oxide, glycidyl
  • the epoxide monomer is an olefin oxide, more preferably an olefin oxide having 2 to 20 carbon atoms, such as for example ethylene oxide, propylene oxide, 1,2-epoxy-butane, or 2,3-epoxybutane.
  • the most preferred monomer is ethylene oxide. Outstanding results are achieved in polymerizing ethylene oxide via that suspension polymerization route.
  • Polymerization of an olefin oxide, preferably ethylene oxide typically does not encompass the preparation of oligomers such as polyethylene glycols and their mono- and diethers having a weight average molecular weight of less than 30,000, as determined by size exclusion chromatography. Accordingly, the term “polymerization of an olefin oxide, preferably ethylene oxide” typically means the preparation of a poly(olefin oxide), preferably poly(ethylene oxide), having a weight average molecular weight of at least 30,000, more preferably at least 50,000, and most preferably at least 80,000, as determined by size exclusion chromatography.
  • the catalytically active species that facilitate the polymerization of the epoxide monomer may be structurally different from the Zn compound of the Zn catalyst (a) and the metal compound (i) as they are present in the inventive catalyst formulation prior to addition to the starting materials of the polymerization reaction.
  • the Zn compound of the Zn catalyst (a) and/or the metal compound (i) may react with other components which are present intentionally (e.g. the optional protonated alcohol (ii)) or unintentionally such as trace amounts of water (to form partially hydrolyzed alkoxides/alcoholates) to result in the catalytically active species.
  • the sequence of adding the Zn catalyst (a), the metal compound (i) and the optional alcohol (ii) to the reaction system is not essential.
  • the Zn catalyst (a), the metal compound (i) and the optional alcohol (ii) may be premixed prior to addition to the reaction system to form a catalyst formulation or they may be added separately, either subsequently or at least two of them simultaneously. Continuous or semi-continuous addition of one or two or all of the Zn catalyst (a), the metal compound (i) and the optional alcohol (ii) is also possible.
  • the Zn catalyst (a) and the metal compound (i) are added to the reaction system is also not crucial.
  • the Zn catalyst (a) is introduced in the form of a solution or suspension which may be obtained either directly from the preparation of the catalyst or by dissolving or dispersing the solid Zn catalyst (a) in an appropriate solvent.
  • suitable solvents include aliphatic hydrocarbons such as isopentane, hexane, octane, decane or dodecane.
  • the metal compound (i) is introduced in the form of a solution or suspension which may be obtained either directly from the preparation of the catalyst or by dissolving or dispersing the solid metal compound (i) in an appropriate solvent.
  • suitable solvents include aliphatic hydrocarbons such as isopentane, hexane, octane, decane or dodecane.
  • the Zn catalyst (a) (including Zn compounds (a1), (a2), and (a3) and preferred embodiments mentioned before) is used in the polymerization of an epoxide monomer, such as ethylene oxide, in an amount providing 1 mol of Zn per 10 to 100,000 mol of epoxide monomer, preferably 1 mol of Zn per 10 to 50,000 mol of epoxide monomer, more preferably 1 mol of Zn per 100 to 20,000 mol of epoxide monomer, even more preferably 1 mol of Zn per 200 to 10,000 mol of epoxide monomer, and most preferably 1 mol of Zn per 250 to 5,000 mol of epoxide monomer or 1 mol of Zn per 250 to 2,500 mol of epoxide monomer.
  • an epoxide monomer such as ethylene oxide
  • the metal compound (i) (including metal compounds (b1) and (b2) and preferred embodiments mentioned before) is preferably used in an amount providing a molar ratio of metal of the metal compound (i) to Zn of the Zn catalyst (a) (including Zn compound (a1), (a2), and (a3) and preferred embodiments mentioned before) within the range of from 0.01:1 to 20:1, more preferably from 0.05:1 to 15:1, even more preferably from 0.05:1 to 10:1, most preferably from 0.05:1 to 8:1 or from 0.1:1 to 8:1.
  • the alcohol is preferably used in an amount providing a molar ratio of alcohol (ii) to metal of the metal compound (i) within the range of from 0.01:1 to 5:1, more preferably from 0.05:1 to 2:1, and most preferably from 0.1:1 to 0.5:1.
  • preferred embodiments of the catalyst formulation comprise the Zn catalyst (a) and the catalyst additive (b) in relative amounts realizing the above ratios, i.e., the Zn catalyst (a) and the metal compound (i) in amounts to provide a molar ratio of metal of the metal compound (i) to Zn of the Zn catalyst (a) within the range of from 0.01:1 to 20:1, more preferably from 0.05:1 to 15:1, even more preferably from 0.05:1 to 10:1, most preferably from 0.05:1 to 8:1 or from 0.1:1 to 8:1, and alcohol (ii) in an amount providing a molar ratio of alcohol (ii) to metal of the metal compound (i) within the range of from 0 to 5:1, preferably 0.01:1 to 5:1, more preferably from 0.05:1 to 2:1, and most preferably from 0.1:1 to 1:1.
  • the polymerization reaction can be conducted over a wide temperature range.
  • Polymerization temperatures can be in the range of from ⁇ 50 to 150° C. and depend on various factors, such as the nature of the epoxide monomer(s) employed, the particular catalyst employed, and the concentration of the catalyst.
  • a typical temperature range is from 0 to 150° C.
  • a reaction temperature below 70° C. is preferred.
  • granular poly(ethylene oxide) can be prepared at a reaction temperature of about 65 to 70° C. the poly(ethylene oxide) product tends to accumulate on the interior surfaces of the reaction equipment. Consequently, it is preferred that the reaction temperature for the preparation of granular poly(ethylene oxide) be in the range of from ⁇ 30 to 65° C. and more preferably from 0 to 60° C.
  • the pressure conditions are not specifically restricted and can be adjusted by the temperature of the polymerization reaction, the vapor pressures of the inert diluents and monomer(s), and the pressure of inerting gas (e.g. nitrogen) introduced into the reactor.
  • inerting gas e.g. nitrogen
  • reaction time will vary depending on the operative temperature, the nature of the epoxide oxide reagent(s) employed, the particular catalyst combination and the concentration employed, the use of an inert diluent, and other factors. Polymerization times can be run from minutes to days depending on the conditions used. Preferred times are 1 to 10 h.
  • the proportions of said epoxides can vary over the entire range.
  • the polymerization reaction preferably takes place in the liquid phase.
  • the polymerization reaction is conducted under an inert atmosphere, e.g. nitrogen. It is also highly desirable to effect the polymerization process under substantially anhydrous conditions Impurities such as water, aldehyde, carbon dioxide, and oxygen which may be present in the epoxide feed and/or reaction equipment should be avoided.
  • the polymers of this invention can be prepared via the bulk polymerization, suspension polymerization, or the solution polymerization route, suspension polymerization being preferred.
  • the polymerization reaction can be carried out in the presence of an inert organic diluent such as, for example, aromatic hydrocarbons, benzene, toluene, xylene, ethylbenzene, and chlorobenzene; various oxygenated organic compounds such as anisole, the dimethyl and diethyl ethers of ethylene glycol, of propylene glycol, and of diethylene glycol; normally-liquid saturated hydrocarbons including the open chain, cyclic, and alkyl-substituted cyclic saturated hydrocarbons such as pentane (e.g.
  • an inert organic diluent such as, for example, aromatic hydrocarbons, benzene, toluene, xylene, ethylbenzene, and chlorobenzene
  • various oxygenated organic compounds such as anisole, the dimethyl and diethyl ethers of ethylene glycol, of propylene glycol, and of diethylene glycol
  • Typical initial concentrations of ethylene oxide in the solvent range from 0.3 to 3 M, preferably from 0.3 to 2.5 M, more preferably from 0.4 to 2 M, and most preferably from 0.5 to 1.5 M (not considering the vapor-liquid equilibrium of ethylene oxide in the system).
  • ethylene oxide polymerizations are extremely exothermic, and practitioners must consider heat removal (or temperature control) in the determination of run conditions.
  • Initial concentrations may be achieved by an ethylene oxide precharge, added before the catalyst addition, or by an ethylene oxide charge following the catalyst introduction to the diluent.
  • the suspension polymerization can be conducted as a batch, semi-continuous, or a continuous process.
  • the single components of the polymerization reaction i.e. the epoxide monomer, the Zn catalyst (a), the metal compound (i), the optional alcohol (ii) and the diluent, if used, may be added to the polymerization system in any practicable sequence as the order of introduction is not crucial for the present invention.
  • the Zn catalyst (a) and monomer be introduced prior to the addition of catalyst additive component (b)
  • it is possible that some fraction of the product will not be influenced by the effect of catalyst additive (b).
  • the present invention provides for new options in the polymerization of epoxide monomers such as ethylene oxide. It is quite surprising that the use of metal compounds (i) which themselves are not competent polymerization catalysts under standard reaction conditions in combination with a Zn catalyst (a) influences the polymerization mechanism. It is further unexpected that in some cases the presence of an additional alcohol (ii) in combination with the metal compounds (i) is not detrimental to the catalyst system as alcohol alone can be a potent catalyst poison, drastically dropping catalyst productivity. In some cases the inventive catalyst additives (b) may increase catalyst reactivity in terms of rate and/or productivity and/or allow for the synthesis of new polymer products.
  • the additive-containing polymerization reactions according to the present invention demonstrate enhanced reaction rate and productivity.
  • the additive-containing reactions according to the present invention demonstrate comparable reaction rate and productivity, while producing lower molecular weight materials, as determined by the viscosity of aqueous solutions.
  • the catalyst additives (b) have the effect of enhancing the reactivity of the Zn catalyst (a) in terms of rate and/or productivity.
  • An increase of catalyst reactivity is typically achieved with embodiments wherein the catalyst additive (b) only comprises the metal alcoholate (i) but no additional alcohol (ii), i.e. no free alcohol has been added to the polymerization reaction.
  • catalyst additives (b) in addition to the Zn catalyst (a) allows to directly synthesize lower molecular weight polymers while sometimes maintaining catalyst activity as measured by polymerization rate and catalyst productivity.
  • the additive (b) acts as molecular weight reducing (or limiting) agent, i.e., some of the catalyst additives (b) are useful to facilitate the production of lower molecular weight polymers, especially lower molecular weight poly(ethylene oxide), if used in combination with the Zn catalyst (a).
  • polymers, especially poly(ethylene oxide) having molecular weights of 100,000 to 2,000,000 based on viscosity determination may be obtained.
  • Exemplary catalyst additives (b) that act as molecular weight control agents are Al alkoxides that are soluble in C 5 -C 14 hydrocarbon solvents such as aluminum sec-butoxide [Al(OC 4 H 9 ) 3 ]. Those exemplary additives (b) are used in combination with the Zn catalyst (a) as described above including the preferred embodiments.
  • molecular weight based on viscosity determination refers to an approximate molecular weight (rough molecular weight estimation) that is assigned to the polymer on the basis of its solution viscosity according to Table 1.
  • Viscosity values which do not exactly fit with the ranges specified in the last column but lie between those ranges correspond to intermediate values of molecular weight.
  • the viscosity is measured on water/isopropyl alcohol solutions of polymer at 25.0° C. using a Brookfield rotational viscometer with the viscometer settings for each molecular weight as indicated in Table 1.
  • 1% aqueous solution viscosity as used in the table means the dynamic viscosity of a 1 weight % solution of the polymer in a mixture of water and isopropyl alcohol. The same definition applies to 2 and 5% solutions.
  • the weight percentage of polymer is based on the weight of water only, i.e. not including the isopropyl alcohol. Preparing the aqueous solutions of the polymers the isopropyl alcohol is added first in order to allow the polymer particles to disperse as individuals before water is added.
  • a second beaker the required amount of high purity water is weighed (594 g for a 1 wt. % solution; 588 g for a 2 wt. % solution and 570 g for a 5 wt. % solution).
  • To the polymer containing beaker is then added 125 mL of anhydrous isopropanol and the resulting mixture is slurried with a mechanical agitator (the agitator and additional experimental details are described more specifically in the above mentioned Dow bulletin).
  • the stirrer is adjusted to move the bottom propeller as close to the bottom of the beaker as possible, and the mixture is stirred at 300-400 rpm in order to form a well distributed slurry.
  • the appropriate viscometer spindle is immersed in the polymer solution, avoiding entrapping air bubbles, and attached to the viscometer shaft. The height is adjusted to allow the solution level to meet the notch on the spindle. The viscometer motor is activated, and the viscosity reading is taken at a specified time interval following the start of the viscometer motor.
  • Solvents used in the examples were purified over activated A2 alumina to remove residual moisture. IsoparTM E and hexanes were also purified over activated Q5 catalyst to remove residual oxygen.
  • the viscosities of the polymers referred to in the examples were measured on water/isopropyl alcohol solutions of polymer at 25.0° C. using a Brookfield rotational viscometer with the viscometer settings as indicated in Table 1. The corresponding solutions were prepared as described above.
  • a zinc alkoxide catalyst was prepared guided by the description provided in U.S. Pat. No. 6,979,722 B2, Example 1.
  • a 250 mL flask was set up in an inert atmosphere glovebox and charged with IsoparTM E (isoparaffinic fluid, CAS 64741-66-8) (80 mL) and diethyl zinc (5.0 mL, 48.8 mmol).
  • IsoparTM E isoparaffinic fluid, CAS 64741-66-8
  • diethyl zinc 5.0 mL, 48.8 mmol
  • 1,4-butanediol 3.5 mL, 39.5 mmol, dried over molecular sieves
  • EO ethylene oxide
  • Ethylene oxide was continuously fed into the reactor until 100 g total had been added. The rate of ethylene oxide addition was adjusted so that the calculated solution concentration of ethylene oxide would stay below 7 wt. %. After 285 min, 1.5 mL of isopropyl alcohol were charged into the reactor and the reactor was cooled. The solid polymer product was isolated by filtration, dried in a vacuum oven over night at room temperature, and stabilized with 500 ppm butylhydroxytoluene (BHT). The poly(ethylene oxide) (PEO) yield was 73.3 g. A 1 wt. % aqueous solution of the polymer product was determined to have a viscosity of 3,400 mPa ⁇ s (spindle no. 2, 2 rpm, 5 min measurement time).
  • EO polymerization was carried out as described in Comparative Example 2a.
  • the catalyst solution was injected into a reactor precharged with 30 g of ethylene oxide. After 268 min, the EO solution concentration was 2.6 wt. %, 1.5 mL of isopropyl alcohol were charged into the reactor at this time and the reactor was cooled.
  • the polymer was isolated and stabilized as described in Comparative Example 2a.
  • the PEO yield was 80.8 g.
  • a 1 wt. % aqueous solution of the polymer product was determined to have a viscosity of 4860 mPa ⁇ s (spindle no. 2, 2 rpm, 5 min measurement time).
  • % aqueous solution of the polymer product was determined to have a viscosity of 20-40 mPa ⁇ s (well below the 1 wt. % analysis scale) while a 5 wt. % aqueous solution gave a viscosity of 1260 mPa ⁇ s (spindle no. 2, 10 rpm, 1 min measurement time).
  • the zinc alkoxide catalyst was prepared as described in Reference Example 1 from 5.12 g of neat diethylzinc (41.5 mmol), 3.06 g of neat 1,4-butanediol (33.9 mmol, dried over molecular sieves), and 3.1 mL of neat anhydrous ethanol (53 mmol).
  • IsoparTM E a mixture of anhydrous n-hexane (20 mL) and anhydrous decane (70 mL) was used.
  • the final catalyst slurry was diluted in anhydrous decane to achieve a concentration of 200 mM.
  • a 300 mL Parr reactor was used to carry out EO polymerization reactions in Examples 5 through 7.
  • the clean reactor was heated to >120° C. overnight under a N 2 purge and cooled prior to reagent loading.
  • Anhydrous n-hexane solvent 180 mL was loaded into the closed, N 2 -sparged reactor from a 300 mL delivery cylinder.
  • CAB-O-SIL® TS-720 fumed silica (383 mg) was added via syringe as a slurry in n-hexane ( ⁇ 15 mL), followed by the additive (also via syringe as an n-hexane solution) and finally (via syringe) 6 mL of a 200 mM catalyst slurry as prepared in Reference Example 4.
  • the reactor was heated to 40° C. and pressured to 76 kPa (11 psi) with N 2 , following which EO was fed into the reactor until the total reactor pressure reached 145 kPa (21 psi).
  • EO polymerization was carried out as described in Comparative Example 5 except that 1.7 mmol of di-s-butoxyaluminoxy-triethoxysilane (commercially available from Geleste) dissolved in 10 mL of n-hexane was added to the reactor prior to the addition of catalyst.
  • the silica amount was 378 mg of CAB-O-SIL® TS-720 fumed silica, and the catalyst amount was the same as in Comparative Example 5.
  • a total of 25.4 g of EO was added to the reactor with a total reaction time of 501 minutes, and 19.0 g of dry PEO product was isolated in the manner described in Comparative Example 5.
  • EO polymerization was carried out as described in Comparative Example 5 except that 1.7 mmol of di-s-butoxyaluminoxy-triethoxysilane (commercially available from Geleste) dissolved in 10 mL of n-hexane was added to the reactor prior to the addition of catalyst.
  • the silica amount was 378 mg of CAB-O-SIL® TS-720 fumed silica, and the catalyst amount was the same as in Comparative Example 5.
  • a total of 24.9 g of EO was added to the reactor with a total reaction time of 515 minutes, and 23.4 g of dry PEO product was isolated in the manner described in Comparative Example 5.
  • the viscosity of a 5 wt. % solution of a 1:1 mixture of the product of Examples 6a and 6b was 90.0 mPa ⁇ s (spindle no. 1, 50 rpm, 0.5 min measurement time).
  • EO polymerization was carried out as described in Comparative Example 5 except that 2.0 mmol of aluminum (di-s-butoxide) ethylacetoacetate (commercially available from Geleste) dissolved in 10 mL of n-hexane was added to the reactor prior to the addition of catalyst.
  • the silica amount was 374 mg of CAB-O-SIL® TS-720 fumed silica, and the catalyst amount was the same as in Comparative Example 5.
  • a total of 26.3 g of EO was added to the reactor with a total reaction time of 176 minutes, and 24.2 g of dry PEO product was isolated in the manner described in Comparative Example 5.
  • EO polymerization was carried out as described in Comparative Example 5 except that 2.0 mmol of aluminum (di-s-butoxide) ethylacetoacetate (commercially available from Geleste) dissolved in 10 mL of n-hexane was added to the reactor prior to the addition of catalyst.
  • the silica amount was 372 mg of CAB-O-SIL® TS-720 fumed silica, and the catalyst amount was the same as in Comparative Example 5.
  • a total of 26.5 g of EO was added to the reactor with a total reaction time of 156 minutes, and 24.6 g of dry PEO product was isolated in the manner described in Comparative Example 5.
  • the viscosity of a 5 wt. % solution of a 1:1 mixture of the product of Examples 7a and 7b was 5,960 mPa ⁇ s (spindle no. 2, 2 rpm, 5 min measurement time).
  • EO polymerization was carried out following as in Comparative Example 2a with modification to the order of addition of zinc catalyst and the aluminum-tri-sec-butoxide additive.
  • Aluminum-tri-sec-butoxide (2.5 mL, 9.7 mmol) was dissolved in anhydrous hexanes (approximately 25 L) and injected into an EO charged reactor (28 g precharge). No evidence of polymer formation was observed until after the zinc alkoxide catalyst (2.4 mmol added by dilution of the 400 mM stock in approximately 25 mL of hexanes) was charged 130 min into the reactor run. Soon after the addition of the zinc catalyst, the solution began to develop the white solid particles characteristic of polyethylene oxide formation in hydrocarbon solvent.
  • FIG. 1 illustrates the EO polymerizations described in Examples 3 and 8.
  • total EO right axis, in grams
  • EO solution concentration left axis, EO wt % as determined by a vapor liquid equilibrium model
  • the aluminum-tri-sec-butoxide additive is not a competent catalyst for the polymerization of EO under these conditions by itself.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Polyethers (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US15/035,411 2013-11-22 2014-11-18 Zinc catalyst/additive system for the polymerization of epoxide monomers Expired - Fee Related US9938374B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US15/035,411 US9938374B2 (en) 2013-11-22 2014-11-18 Zinc catalyst/additive system for the polymerization of epoxide monomers

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US201361907410P 2013-11-22 2013-11-22
US15/035,411 US9938374B2 (en) 2013-11-22 2014-11-18 Zinc catalyst/additive system for the polymerization of epoxide monomers
PCT/US2014/066080 WO2015077210A1 (en) 2013-11-22 2014-11-18 Zinc catalyst / additive system for the polymerization of epoxide monomers

Publications (2)

Publication Number Publication Date
US20160280853A1 US20160280853A1 (en) 2016-09-29
US9938374B2 true US9938374B2 (en) 2018-04-10

Family

ID=52232397

Family Applications (1)

Application Number Title Priority Date Filing Date
US15/035,411 Expired - Fee Related US9938374B2 (en) 2013-11-22 2014-11-18 Zinc catalyst/additive system for the polymerization of epoxide monomers

Country Status (7)

Country Link
US (1) US9938374B2 (ja)
EP (1) EP3071628B1 (ja)
JP (1) JP6510515B2 (ja)
KR (1) KR20160089381A (ja)
CN (1) CN105705552A (ja)
CA (1) CA2930729A1 (ja)
WO (1) WO2015077210A1 (ja)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015151598A1 (ja) 2014-03-31 2015-10-08 住友精化株式会社 アルキレンオキシド重合体の製造方法
EP3771593B1 (en) 2019-07-30 2023-04-05 Volvo Car Corporation Method and system for predictive battery thermal management in an electric vehicle

Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3313740A (en) 1962-09-26 1967-04-11 Gen Tire & Rubber Co Expoxide polymerization catalysts, their preparation and their use
US3459685A (en) 1967-03-28 1969-08-05 Jefferson Chem Co Inc Polymerization of cyclic alkylene oxides with catalyst systems of a polymeric aluminum alcoholate and an organometallic
GB1197986A (en) 1967-10-27 1970-07-08 Seittesu Kagaku Company Ltd Process for producing High Molecular Weight Polymers of Alkylene Oxides
US3520827A (en) 1966-12-02 1970-07-21 Inst Francais Du Petrole Process for manufacturing new polymerization catalysts,the resulting new catalysts and their uses
US3542750A (en) 1969-05-05 1970-11-24 Jefferson Chem Co Inc Catalyst for the polymerization of cyclic alkylene oxides
US3607785A (en) 1967-11-21 1971-09-21 Inst Francais Du Petrole Polymerization catalysts,their manufacture and use for polymerizing cyclic ethers
DE1667275A1 (de) 1967-11-03 1972-03-09 Seitetsu Kagaku Co Ltd Verfahren und Katalysator zur Herstellung von hochmolekularen Alkylenoxydpolymerisaten
US4375564A (en) 1981-12-23 1983-03-01 Shell Oil Company Alkoxylation process
US4667013A (en) 1986-05-02 1987-05-19 Union Carbide Corporation Process for alkylene oxide polymerization
EP0239973A2 (en) 1986-03-31 1987-10-07 Union Carbide Corporation Catalyst and process for alkylene oxide polymerization
US5326852A (en) 1991-07-11 1994-07-05 Sumitomo Seika Chemicals Co., Ltd. Method for production of alkylene oxide polymers
US6084059A (en) 1998-04-03 2000-07-04 Nippon Shokubai Co., Ltd. Production process for organometallic fine particle and catalyst for polymerization
US6458918B1 (en) 1997-11-03 2002-10-01 Bayer Aktiengesellschaft Method for producing partially crystalline polyether polyols
US6979722B2 (en) 2001-03-07 2005-12-27 Sumitomo Seika Chemicals Co., Ltd. Process for production of alkyllene oxide polymers
US20060264601A1 (en) * 2005-05-20 2006-11-23 Nippon Shokubai Co., Ltd. Method for production of alkylene oxide based polymer
US20160289380A1 (en) * 2013-11-22 2016-10-06 Dow Global Technologies Llc Zinc catalyst/additive system for the polymerization of epoxide monomers
US20160289381A1 (en) * 2013-11-22 2016-10-06 Dow Global Technologies Llc Zinc catalyst/additive system for the polymerization of epoxide monomers

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4923839B1 (ja) * 1970-12-28 1974-06-18
JP5817150B2 (ja) * 2011-03-04 2015-11-18 東ソー株式会社 亜鉛アルコキシ錯体及びその製造法、並びにその用途

Patent Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3313740A (en) 1962-09-26 1967-04-11 Gen Tire & Rubber Co Expoxide polymerization catalysts, their preparation and their use
US3520827A (en) 1966-12-02 1970-07-21 Inst Francais Du Petrole Process for manufacturing new polymerization catalysts,the resulting new catalysts and their uses
US3459685A (en) 1967-03-28 1969-08-05 Jefferson Chem Co Inc Polymerization of cyclic alkylene oxides with catalyst systems of a polymeric aluminum alcoholate and an organometallic
GB1197986A (en) 1967-10-27 1970-07-08 Seittesu Kagaku Company Ltd Process for producing High Molecular Weight Polymers of Alkylene Oxides
DE1667275A1 (de) 1967-11-03 1972-03-09 Seitetsu Kagaku Co Ltd Verfahren und Katalysator zur Herstellung von hochmolekularen Alkylenoxydpolymerisaten
US3607785A (en) 1967-11-21 1971-09-21 Inst Francais Du Petrole Polymerization catalysts,their manufacture and use for polymerizing cyclic ethers
US3542750A (en) 1969-05-05 1970-11-24 Jefferson Chem Co Inc Catalyst for the polymerization of cyclic alkylene oxides
US4375564A (en) 1981-12-23 1983-03-01 Shell Oil Company Alkoxylation process
EP0239973A2 (en) 1986-03-31 1987-10-07 Union Carbide Corporation Catalyst and process for alkylene oxide polymerization
US4667013A (en) 1986-05-02 1987-05-19 Union Carbide Corporation Process for alkylene oxide polymerization
US5326852A (en) 1991-07-11 1994-07-05 Sumitomo Seika Chemicals Co., Ltd. Method for production of alkylene oxide polymers
US6458918B1 (en) 1997-11-03 2002-10-01 Bayer Aktiengesellschaft Method for producing partially crystalline polyether polyols
US6084059A (en) 1998-04-03 2000-07-04 Nippon Shokubai Co., Ltd. Production process for organometallic fine particle and catalyst for polymerization
US6979722B2 (en) 2001-03-07 2005-12-27 Sumitomo Seika Chemicals Co., Ltd. Process for production of alkyllene oxide polymers
US20060264601A1 (en) * 2005-05-20 2006-11-23 Nippon Shokubai Co., Ltd. Method for production of alkylene oxide based polymer
US20160289380A1 (en) * 2013-11-22 2016-10-06 Dow Global Technologies Llc Zinc catalyst/additive system for the polymerization of epoxide monomers
US20160289381A1 (en) * 2013-11-22 2016-10-06 Dow Global Technologies Llc Zinc catalyst/additive system for the polymerization of epoxide monomers

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
M. Osgan, Bimetallic Oxo-Alkoxides as Catalysts for the Insertion Polymerization of Epoxides, Polymer Letters, 1967, vol. 5, pp. 789-792.
V. Rejsek et al., Polymerization of ethylene oxide initiated by lithium derivatives via the monomer-activated approach, Polymer, 2010, 51, pp. 5674-5679.

Also Published As

Publication number Publication date
US20160280853A1 (en) 2016-09-29
EP3071628B1 (en) 2018-01-10
KR20160089381A (ko) 2016-07-27
JP6510515B2 (ja) 2019-05-08
CN105705552A (zh) 2016-06-22
WO2015077210A1 (en) 2015-05-28
CA2930729A1 (en) 2015-05-28
JP2017503034A (ja) 2017-01-26
EP3071628A1 (en) 2016-09-28

Similar Documents

Publication Publication Date Title
EP1046663B1 (en) Polymerization of cyclic ethers using selected metal compound catalysts
US20090057608A1 (en) Alkoxylate composition and a process for preparing the same
US9938374B2 (en) Zinc catalyst/additive system for the polymerization of epoxide monomers
ES2941289T3 (es) Proceso de polimerización de poliéter
US9624343B2 (en) Zinc catalyst/additive system for the polymerization of epoxide monomers
US9879115B2 (en) Zinc catalyst/additive system for the polymerization of epoxide monomers
US2971988A (en) Metal-amide alcoholates and process of preparation
CN118103137A (zh) 使用大环双金属催化剂与双金属氰化物催化剂的混合物通过环氧化物和co2共聚制备表面活性剂的方法
ES2961155T3 (es) Proceso de polimerización de poliéter
US3144417A (en) Polymerization of epoxides
EP4423168A1 (en) Polyether polymerization process
TW202317661A (zh) 聚醚聚合方法
WO2024137254A1 (en) Alkoxylation processes using phosphorus and double metal cyanide catalysts

Legal Events

Date Code Title Description
AS Assignment

Owner name: DOW GLOBAL TECHNOLOGIES LLC, MICHIGAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:DAVIS, ANNA V.;NICKIAS, PETER N.;REEL/FRAME:045439/0138

Effective date: 20140515

STCF Information on status: patent grant

Free format text: PATENTED CASE

AS Assignment

Owner name: THE DOW CHEMICAL COMPANY, MICHIGAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:DOW GLOBAL TECHNOLOGIES LLC;REEL/FRAME:054531/0001

Effective date: 20181101

Owner name: DDP SPECIALTY ELECTRONIC MATERIALS US, LLC., DELAWARE

Free format text: CHANGE OF LEGAL ENTITY;ASSIGNOR:DDP SPECIALTY ELECTRONIC MATERIALS US, INC.;REEL/FRAME:054530/0384

Effective date: 20201101

Owner name: DDP SPECIALTY ELECTRONIC MATERIALS US, INC., DELAWARE

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:THE DOW CHEMICAL COMPANY;REEL/FRAME:054533/0001

Effective date: 20181101

Owner name: NUTRITION & BIOSCIENCES USA 1, LLC, NEW YORK

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:DDP SPECIALTY ELECTRONIC MATERIALS US, LLC.;REEL/FRAME:054533/0575

Effective date: 20201101

FEPP Fee payment procedure

Free format text: MAINTENANCE FEE REMINDER MAILED (ORIGINAL EVENT CODE: REM.); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

LAPS Lapse for failure to pay maintenance fees

Free format text: PATENT EXPIRED FOR FAILURE TO PAY MAINTENANCE FEES (ORIGINAL EVENT CODE: EXP.); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

STCH Information on status: patent discontinuation

Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362

FP Lapsed due to failure to pay maintenance fee

Effective date: 20220410